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Volumn 105, Issue 16, 1996, Pages 6997-7010

The isotope effect in solvation dynamics and nonadiabatic relaxation: A quantum simulation study of the photoexcited solvated electron in D2O

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EID: 0142089293     PISSN: 00219606     EISSN: None     Source Type: Journal    
DOI: 10.1063/1.471989     Document Type: Article
Times cited : (85)

References (83)
  • 4
    • 0002627110 scopus 로고
    • edited by M. P. Allen and D. J. Tildesely Kluwer Academic, Dodrecht
    • D. F. Coker, in Computer Simulations in Chemical Physics, edited by M. P. Allen and D. J. Tildesely (Kluwer Academic, Dodrecht, 1993), p. 315.
    • (1993) Computer Simulations in Chemical Physics , pp. 315
    • Coker, D.F.1
  • 36
    • 85033069579 scopus 로고    scopus 로고
    • note
    • Note that the calculated equilibrium absorption spectrum is blueshifted by ≥0.5 eV from the experimental one, a result likely due to the lack of inclusion of electronic polarizability of the solvent (see, e.g., Ref. 18). In previous work, we subtracted this shift in the equilibrium spectrum when comparing the experimental and calculated nonequilibrium spectral transients. In the present work, all spectral calculations are presented without this shift taken into account, directly as computed during the simulations.
  • 37
    • 85033035142 scopus 로고    scopus 로고
    • note
    • 2O, we expected rapid equilibration following the nonadiabatic relaxation and elected to save computational resources by terminating trajectories 0.5 ps after the radiationless transition. A posteriori justification for this assumption is provided in Fig. 6.
  • 45
    • 85033048359 scopus 로고    scopus 로고
    • 1/2. This is likely the result of significant translation-rotation coupling
    • 1/2. This is likely the result of significant translation-rotation coupling.
  • 52
    • 85033048809 scopus 로고    scopus 로고
    • private communication
    • R. D. J. Miller (private communication).
    • Miller, R.D.J.1
  • 55
    • 85033040975 scopus 로고    scopus 로고
    • unpublished data
    • A calculation of the resonance Raman spectrum of the hydrated electron also bears this out: resonance enhancement is seen only for the low frequency, intermolecular solvent motions. W. B. Bosnia, B. J. Schwartz and P. J. Rossky (unpublished data).
    • Bosnia, W.B.1    Schwartz, B.J.2    Rossky, P.J.3
  • 57
    • 85033069997 scopus 로고    scopus 로고
    • note
    • It would be interesting, for example, to compare the solvation dynamics resulting from exciting a neutral-to-singly charged atomic species as explored in Ref. 56 and those resulting from excitation of a singly charged to doubly charged species. In the latter case, the orientation of the solvent is already nearly optimal for the doubly charged species, so most of the solvation should result from a slight inward collapse of the first solvation shell due to the enhanced Coulomb attraction. For this case, there would be no symmetry change to the charge distribution and hence, negligible reorientational motion in the solvent relaxation.
  • 59
    • 85033065435 scopus 로고    scopus 로고
    • Note that for the hydrated electron and idealized state symmetry, the leading order change in charge distribution would be the quadrupole; see Ref. 7
    • Note that for the hydrated electron and idealized state symmetry, the leading order change in charge distribution would be the quadrupole; see Ref. 7.
  • 66
    • 85033042635 scopus 로고    scopus 로고
    • This is not in accord with the "standard picture" of solvation, which holds that rotational motions of individual first shell solvent molecules dominate the early time solvent response
    • This is not in accord with the "standard picture" of solvation, which holds that rotational motions of individual first shell solvent molecules dominate the early time solvent response.
  • 70
    • 33751157393 scopus 로고
    • We note that caution is warranted when extrapolating from OKE data, which reflects the solvent polarizability, to solvation dynamics, which depends on the solvent polarization. See, e.g., H. P. Deuel, P. J. Cong, and J. D. Simon, J. Phys. Chem. 98, 12600 (1994).
    • (1994) J. Phys. Chem. , vol.98 , pp. 12600
    • Deuel, H.P.1    Cong, P.J.2    Simon, J.D.3
  • 72
    • 0000131335 scopus 로고
    • A different model, in which nonadiabatic relaxation happens rapidly while the gap is large and significant relaxation then takes place on the ground state is consistent with the behavior of solvated electrons in alcohols: see P. K. Walhout, J. C. Alfano, Y. Kimura, C. Silva, and P. F. Barbara, Chem. Phys. Lett. 232, 135 (1995).
    • (1995) Chem. Phys. Lett. , vol.232 , pp. 135
    • Walhout, P.K.1    Alfano, J.C.2    Kimura, Y.3    Silva, C.4    Barbara, P.F.5
  • 74
    • 85033034869 scopus 로고    scopus 로고
    • note
    • By linear response, we mean simply that the regression of fluctuations at equilibrium is the same as the relaxation following an external perturbation. Thus, it is possible for both the upwards and downwards transitions to follow linear response, even though the two responses are dissimilar, since the final equilibrium fluctuations in the excited state can be different from the initial equilibrium fluctuations in the ground state.
  • 76
    • 0000593564 scopus 로고
    • and references therein
    • B. Space and D. F. Coker, J. Chem. Phys. 96, 652 (1992), and references therein.
    • (1992) J. Chem. Phys. , vol.96 , pp. 652
    • Space, B.1    Coker, D.F.2
  • 83
    • 85033061701 scopus 로고    scopus 로고
    • note
    • 2O transients due to the error in choice of quantum decoherence time actually agree better with the experimental results.


* 이 정보는 Elsevier사의 SCOPUS DB에서 KISTI가 분석하여 추출한 것입니다.